EP2377870A1 - Nouveaux phosphonates et compositions de résine styrénique ignifugeantes les incluant - Google Patents

Nouveaux phosphonates et compositions de résine styrénique ignifugeantes les incluant Download PDF

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EP2377870A1
EP2377870A1 EP09835150A EP09835150A EP2377870A1 EP 2377870 A1 EP2377870 A1 EP 2377870A1 EP 09835150 A EP09835150 A EP 09835150A EP 09835150 A EP09835150 A EP 09835150A EP 2377870 A1 EP2377870 A1 EP 2377870A1
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ether
poly
styrenic resin
phenylene
weight
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EP09835150A
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German (de)
English (en)
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EP2377870A4 (fr
EP2377870B1 (fr
Inventor
Beom Jun Joo
Man Suk Kim
Woo Joong Kim
Seon Ae Lee
Byun Kun Lee
Myoung Jun Kim
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Cheil Industries Inc
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Cheil Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene

Definitions

  • the present invention relates to novel phosphonate based compound and a flame retardant styrenic resin composition including the same. More particularly, the present invention relates to novel phosphonate based compound and a non-halogen flame retardant styrenic resin composition improved flame retardancy by adding the phosphonate based compound to a blend of styrenic resin copolymer and polyphenylene resin.
  • styrenic resins have good processability and mechanical properties and have accordingly been used to produce housing parts for many electrical and electronic goods.
  • styrenic resins can be readily ignited further can readily spread fire.
  • styrenic resins are subject to various mandatory controls on flammability for safety reasons in countries such as the United States, Japan and Europe, and are required to have high flame retardancy to meet the Underwriter's Laboratories Standard for use in the housings of electrical and electronic appliances.
  • a widely used and known method for imparting good flame retardancy to styrenic resin comprises adding a halogen-containing compound as a flame retardant to a rubber-modified styrenic resin and adding an antimony-containing compound as a flame retardant aid.
  • halogen-containing compounds used to impart flame retardancy include polybromodiphenyl ether, tetrabromobisphenol-A, epoxy compounds substituted with bromine, chlorinated polyethylene, and the like.
  • Antimony trioxide or antimony pentaoxide is commonly used as an antimony-containing compound.
  • halogen- and antimony-containing compound When a halogen- and antimony-containing compound is used to improve flame retardancy of resins, a desired degree of flame retardancy can readily be imparted to the resulting products without significantly degrading the physical properties thereof.
  • hydrogen halide gases released by halogen-containing compounds during processing can have fatal effects on the human body.
  • polybromodiphenyl ether which is widely used as a halogen-containing flame retardant, may produce toxic gases such as dioxin or furan during combustion.
  • Rubber-modified styrenic resins generally have little remaining char during combustion, and thus it is hard to impart flame retardancy to such resins in their solid state ( Journal of Applied Polymer Science, 1998, vol. 68, p. 106 ). Therefore, it may be necessary to add a char forming agent to a rubber-modified styrenic resin so that char can be formed in order to obtain desirable flame retardancy, which can negatively impart other properties of the resin.
  • a well known and widely used method of imparting flame retardancy without using halogen-containing flame retardants uses a phosphate ester flame retardant.
  • relatively high amounts of phosphate ester flame retardants or flame retardant aids are required to obtain sufficient flame retardancy.
  • WO 2008114858 , WO 2008108485 and US 2008/0227884 refer to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which is a phosphonate based cyclic compound, and a reactive flame retardant resin using the same.
  • 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide is only used as a phosphorous-containing flame retardant hardener for imparting flame retardancy to thermoset(crosslinking and hardening) resins. They don't disclose a method of synthesizing phosphonate based flame retardant cyclic compound by adding different derivatives to 1,1'-bi-2-naphthol compound and a thermoplastic resin composition including the same.
  • the present invention provides a novel phosphonate based compound which can be added to a resin composition to provide flame resistance.
  • the present invention further provides a flame resistant styrenic resin composition including a novel phosphonate based compound which can have fire stability.
  • the present invention further provides an environmentally-friendly styrenic resin composition which includes a halogen-free flame retardant and which can have excellent flame resistance as compared to a composition including a phosphate ester flame retardant.
  • the present invention provides a phosphonate based compound represented by the following Chemical Formula 1. wherein in the above Chemical Formula 1, R 2 is C 1 to C 4 alkyl, phenymethyl or cyanomethyl.
  • R 2 is phenylmethyl or cyanomethyl.
  • the present invention further provides a flame resistant styrenic resin composition
  • a flame resistant styrenic resin composition comprising: a styrenic resin (A), a polyphenylene ether resin (B) and a phosphonate based compound (C) represented by the above Chemical Formula 1.
  • the flame resistant styrenic resin composition may comprise about 70 to about 99 percent by weight of the styrenic resin (A), about 1 to about 30 percent by weight of the polyphenylene ether resin (B), and about 0.5 to about 30 parts by weight of the phosphonate based compound (C) represented by the above Chemical Formula 1, based on about 100 parts by weight of the base resin (A)+(B).
  • the flame resistant styrenic resin composition may further comprise about 1 to about 20 parts by weight of a phosphorus flame retardant (D), based on about 100 parts by weight of the base resin (A)+(B).
  • D phosphorus flame retardant
  • the phosphorus flame retardant (D) may be an aromatic phosphorus ester compound (D)-1, a metal salt compound of an alkyl phosphonic acid (D)-2 which has a particle size of less than about 10 ⁇ m, or a combination thereof.
  • the present invention provides a phosphonate based compound represented by the following Chemical Formula 1. wherein in the above Chemical Formula 1, R 2 is C 1 to C 4 alkyl, phenymethyl or cyanomethyl.
  • R 2 is phenylmethyl or cyanomethyl.
  • the phosphonate based compound represented by the Chemical Formula 1 can be synthesized according to Scheme 1. wherein in the above Scheme 1, R 1 is C 1 to C 4 alkyl, and R 2 is the same as described above.
  • (1,1'-binaphthalene-2,2'-dioxy)phenylmethyl phosphonate or (1,1'-binaphthalene-2,2'-dioxy)cyanomethyl phosphonate can be prepared by preparing an intermediate which is prepared by a dechlorination reaction of phosphorus trichloride, aryl-alcohol and ethanol, and reacting the intermediate and a benzylbromide or a bromo acetonitrile.
  • the (1,1'-binaphthalene-2,2'-dioxy)phenylmethyl phosphonate and (1,1'-binaphthalene-2,2'-dioxy)phenylmethyl phosphonate may prepared as follows.
  • An intermediate such as (1,1'-binaphthalene-2,2'-dioxy)ethyl phosphite can be prepared by stirring about 1 to about 3 equivalence ratio of phosphorus trichloride, for example 1 equivalence ratio, about 1 equivalence ratio of 1,1'-bi-2-naphthol and about 1 equivalence ratio of ethanol, in the presence of nitrogen at room temperature.
  • the present invention provides a flame resistant styrenic resin composition
  • a flame resistant styrenic resin composition comprising a styrenic resin (A), a polyphenylene ether resin (B) and a phosphonate based compound (C) represented by Chemical Formula 1.
  • the flame resistant styrenic resin composition may comprise about 70 to about 99 percent by weight of the styrenic resin (A), about 1 to about 30 percent by weight of the polyphenylene ether resin (B), and about 0.5 to about 30 parts by weight of the phosphonate based compound (C) represented by the above Chemical Formula 1, based on about 100 parts by weight of the base resin (A)+(B).
  • the flame resistant styrenic resin composition may further comprise about 1 to about 20 parts by weight of a phosphorus flame retardant (D), based on about 100 parts by weight of the base resin (A)+(B).
  • D phosphorus flame retardant
  • the styrenic resin (A) that can be used in the resin composition of the present invention can be prepared by mixing a rubber, an aromatic mono-alkenyl monomer, optionally an alkyl ester monomer, and optionally an unsaturated nitrile monomer and thermally polymerizing the mixture or polymerizing the mixture with an initiator
  • Examples of the rubber used in the polymerization of the styrenic resin (A) can include, without limitation, polybutadiene, polyisoprene, styrene-butadiene copolymer, alkyl acrylate rubber and the like, and combinations thereof.
  • the amount of the rubber used can be about 3 to about 30% by weight, for example about 5 to about 15% by weight, based on the total weight of the styrenic resin.
  • the monomer for preparing the styrenic resin (A) is an aromatic mono-alkenyl monomer.
  • the amount of the aromatic mono-alkenyl monomer used can be about 70 to about 97% by weight, for example about 85 to about 95% by weight, based on the total weight of the styrenic resin.
  • Other monomers copolymerizable with the aromatic mono-alkenyl monomer such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide and the like, or a combination thereof can also be added to the monomers and polymerized to impart properties such as chemical resistance, processability and heat resistance to the polymer.
  • These other monomers can be added in an amount of about 0 to about 40 parts by weight per 100 parts by weight of a total weight of the styrenic resin.
  • the styrenic resin (A) can be can be polymerized with heat and no initiator or can be polymerized in the presence of an initiator.
  • the initiator may include one or more selected from the group consisting of organic peroxides such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide and cumene hydroperoxide, azo compounds such as azobisisobutyronitrile, and the like, and combinations thereof.
  • Polymerization methods for making the styrenic resin (A) can include bulk polymerization, suspension polymerization, emulsion polymerization or a combination thereof.
  • the bulk polymerization may be used.
  • the average size of rubber particles can range from about 0.1 to about 4.0 ⁇ m to optimize physical properties when blending a styrenic resin and a polyphenylene ether resin.
  • the resin composition according to the present invention may employ a polyphenylene ether resin (B) with the styrenic resin (A) as a base resin to further improve flame retardancy and heat resistance.
  • the polyphenylene ether resin (B) can include, without limitation, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, copolymer of poly(2,6-dimethyl-1,4-phenylene) ether and poly(2,3,6-trimethyl-1,4-phenylene) ether
  • a copolymer of poly(2,6-dimethyl-1,4-phenylene) ether and poly(2,3,6-trimethyl-1,4-phenylene) ether or poly(2,6-dimethyl-1,4-phenylene) ether can be used.
  • poly(2,6-dimethyl-1,4-phenylene) ether can be used.
  • the degree of polymerization of the polyphenylene ether resin (B) is not limited specifically, but can vary depending on factors such as heat-stability or processability of the resin composition.
  • the intrinsic viscosity of the polyphenylene ether resin may be in the range of about 0.2 to about 0.8 as measured in chloroform solvent at 25° C.
  • the base resin composition may comprise about 70 to about 99% by weight of the styrenic resin (A) and about 1 to about 30% by weight of the polyphenylene ether resin (B).
  • the polyphenylene ether resin (B) can be used in an amount of about 15 to about 30% by weight, based on a total weight of the base resin (A)+(B).
  • flame retardancy may tend to decrease.
  • the polyphenylene ether resin (B) is used in an amount of greater than about 30% by weight, processability can be deteriorated.
  • the phosphonate based compound (C) represented by the above Chemical Formula 1 can be used inan amout about 0.5 to about 30 parts by weight, for example about 5 to about 25 parts by weight, based on about 100 parts by weight of the base resin comprising the styrenic resin (A) and the polyphenylene ether resin (B).
  • the phosphonate based compound (C) represented by the above Chemical Formula 1 is used in an amount of less than about 0.5 parts by weight, flame retardancy tends to decrease.
  • flame retardancy tends to increase but physical properties of the total resin such as mechanical strength can be deteriorated.
  • R 2 is C 1 to C 4 alkyl, phenymethyl or cyanomathyl.
  • the phosphonate based compound (C) represented by the above Chemical Formula 1 can be (1,1'-binaphthalene-2,2'-dioxy)phenylmethyl phosphonate or (1,1'-binaphthalene-2,2'-dioxy)cyanomethyl phosphonate.
  • the flame resistant styrenic resin composition may further comprise a phosphorus flame retardant (D).
  • the phosphorus flame retardant (D) may be an aromatic phosphate ester compound (D)-1, a metal salt compound of an alkyl phosphonic acid (D)-2 which has a particle size of less than about 10 ⁇ m, or a combination thereof.
  • the phosphorus flame retardant (D) can be used in an amount of about 1 to about 20 parts by weight, based on about 100 parts by weight of the base resin (A)+(B).
  • the phosphonate based compound (C) can be used in an amount of about 1 to about 20 parts by weight, based on about 100 parts by weight of the base resin (A)+(B).
  • the aromatic phosphate ester compound used in the present invention can have a structure represented by the following Formula 2. wherein R 30 , R 4 , R 5 , R 3 ', R 4 ', R 5 ', R 3 ", R 4 ", R 5 ", R 3 “', R 4 “' and R 5 “' are each independently hydrogen or C 1 -C 4 alkyl; X is C 6 -C 20 aryl or C 1 -C 4 alkyl-substituted C 6 -C 20 aryl; and n is an integer of 0 to 4.
  • X may be a derivative of a dialcohol such as resorcinol, hydroquinol or bisphenol-A.
  • examples of the compound represented by Formula 2 can include, without limitation, triphenyl phosphate, tri(2,6-dimethyl) phosphate, and the like, and where n is 1, examples of the compound can include, without limitation, resorcinol bis(diphenyl) phosphate, resorcinol bis(2,6-dimethyl phenyl) phosphate, resorcinol bis(2,4-ditertiary butyl phenyl) phosphate, hydroquinol bis(2,6-dimethyl phenyl) phosphate, hydroquinol bis(2,4-ditertiary butyl phenyl) phosphate, and the like.
  • the aromatic phosphate ester compound (D)-1 can be used alone or in combination thereof.
  • the metal salt compound of alkyl phosphonic acid used in the present invention can have a structure represented by the following Formula 3 and have a particle size of less than about 10 ⁇ m.
  • each R is independently C 1 -C 6 alkyl, C 1 -C 6 cylcloalkyl or C 6 -C 10 aryl;
  • M is a metal such as Al, Zn, Ca; and
  • n is an integer of 2 or 3.
  • each R may be independently methyl, ethyl, propyl, butyl or phenyl.
  • M may be Al or Zn.
  • the resin composition of the present invention can be prepared by conventional methods employed in the manufacture of resin compositions.
  • the resin composition according to the present invention may further include one or more additives selected without limitation from plasticizers, heat stabilizers, antioxidants, compatibilizers, light-stabilizers, inorganic additives, pigments, dyes and the like, and combinations thereof.
  • the inorganic additives may include asbestos, glass fiber, talc, ceramic, sulfate and the like, and combinations thereof.
  • the one or more additives may be used in an amount of less than about 30 parts by weight based on the total weight of the resin composition.
  • the present invention provides a molded article prepared from the flame resistant styrenic resin composition of the present invention.
  • the molded article may have excellent impact strength and flame resistance and can be environmentally-friendly.
  • Fig 1 represents the results of 1H-NMR analysis of (1,1'-binaphthalene-2,2'-dioxy)phenylmethyl phosphonate prepared by the above method.
  • Fig 2 represents the results of 1H-NMR analysis of (1,1'-binaphthalene-2,2'-dioxy)cyanomethyl phosphonate prepared by the above method.
  • the components in amounts shown in the following Table 1 are extruded through a conventional extruder at about 240 °C to prepare pellets. After the prepared pellets are dried, the pellets are injected under conditions of a molding temperature of 230 °C and a tool temperature of 50 °C. Then, flame resistant samples are prepared. The flame resistance of prepared samples is measured according to UL 94 VB with a thickness of 1/8" and the impact strength is measured according to ASTM D256.
  • Comparative Examples are prepared in the same manner as the Examples above except the Comparative Examples include the components in the amounts shown in the following Table 1. The results are shown in the following Table 1. [Table 1] Examples Comparative Examples 1 2 3 4 1 2 3 HIPS 75 75 75 75 75 75 75 PPE 25 25 25 25 25 25 25 25 25 (1,1'-binaphthalene-2,2'-dioxy) phenylmethyl phosphonate 5 20 - - - - - (1,1'-binaphthalene-2,2'-dioxy) cyanomethyl phosphonate - - 5 20 - - - aromatic phosphorous ester 15 - 15 - 15 10 20 metal salt of alkyl phosphonic acid - - - - 5 - - UL 94 flame resistance (1/8") V-1 V-1 V-0 V-1 V-1 fail V-1 Total burning time 70 110 37 100 103 - 120 IZOD 4.0 7.5 4.2 7.6 3.4 4.5 4.7 4.7
  • IZOD results of examples 1 and 3 are superior to that of comparative examples 1 and IZOD results of examples 2 and 4 are also superior to that of comparative examples 3. Therefore, when a phosphonate based compound represented by the following Chemical Formula 1 as a flame retardant, flame retardancy can be excellent and impact strength can also be improved at the same time.
  • the flame resistant styrenic resin composition including the phosphonate compound of the present invention can have an excellent impact strength and flame resistance and is environmentally-friendly.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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EP09835150.5A 2008-12-26 2009-07-23 Nouveaux phosphonates et compositions de résine styrénique ignifugeantes les incluant Active EP2377870B1 (fr)

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KR1020080134763A KR101055683B1 (ko) 2008-12-26 2008-12-26 신규한 포스포네이트계 화합물 및 이를 포함하는 난연성 스티렌계 수지 조성물
PCT/KR2009/004106 WO2010074384A1 (fr) 2008-12-26 2009-07-23 Nouveaux phosphonates et compositions de résine styrénique ignifugeantes les incluant

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EP2377870A1 true EP2377870A1 (fr) 2011-10-19
EP2377870A4 EP2377870A4 (fr) 2012-04-25
EP2377870B1 EP2377870B1 (fr) 2013-12-18

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KR101055683B1 (ko) 2008-12-26 2011-08-09 제일모직주식회사 신규한 포스포네이트계 화합물 및 이를 포함하는 난연성 스티렌계 수지 조성물
KR101606240B1 (ko) 2013-06-27 2016-03-24 제일모직주식회사 난연성 열가소성 공중합체, 그 제조방법 및 이를 포함하는 성형품

Citations (1)

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GB1528371A (en) * 1976-02-12 1978-10-11 Courtaulds Ltd Filaments containing flame-retardant phosphonates and phosphonates for use therein

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GB1528371A (en) * 1976-02-12 1978-10-11 Courtaulds Ltd Filaments containing flame-retardant phosphonates and phosphonates for use therein

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Title
DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 3 March 2009 (2009-03-03), KASTHURIAH, MADDALI ET AL: "Synthesis of dinaphtho-dioxaphosphepin-4-oxides, epoxides and bisphosphonates", XP002671446, retrieved from STN Database accession no. 2009:510386 -& KASTHURIAH, MADDALI ET AL: "Synthesis of dinaphtho-dioxaphosphepin-4-oxides, epoxides and bisphosphonates", CHINESE JOURNAL OF CHEMISTRY , 27(2), 408-412 CODEN: CJOCEV; ISSN: 1001-604X, 3 March 2009 (2009-03-03), XP002671447, *
See also references of WO2010074384A1 *

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EP2377870A4 (fr) 2012-04-25
US8329791B2 (en) 2012-12-11
WO2010074384A1 (fr) 2010-07-01
US20110251313A1 (en) 2011-10-13
KR101055683B1 (ko) 2011-08-09
KR20100076646A (ko) 2010-07-06
EP2377870B1 (fr) 2013-12-18

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